Motor fuel



latented July 11,1939 Q mm? STATES;

PATENT .orrics MOTOR ml.

nm v. and Johan c. n. oosterhout, Port Arthur; Ten, asslgnors to TheTexas Company, V New York, N.-!', a corporation of Delaware No llrawlng.Application October 12, 1934, r

This invention relates to motor fuels and has to. do particularly withthe treatment of antiknock motor fuelscontaining an anti-knockreegentjby the provision in the fuel of certain re- ;5 'agents whichwill prevent or. retard deterioration it that many gasolines containingtetraethyl lead anti-knock reagent are particularly unstable in sunlightand in a relatively short time become cloudy and even form whitedeposits in the cascline bowls or other dispensing or storing equip- ;3ment.' Furthermore; many of the present day gasoiines of high anti-knockvalue contain cracked hydrocarbons in substantial proportions andthe'presence of suclrwunsaturated hydrocarbons often causes the productto depreciate in, anti-knock value 'and tend to form colored.

and gummy bodies in sunlight and in storage.

gAlso, certain gasolines have a-relatively high sul-,

(on. 44 -9) v A further object of the invention. is to treatgasolinesof-relatively-high sulfur content and tending to be unstable insunlight, particularly when contaig a lead anti-knock reagent, to

improve the normal stability of such products.

' In accordance with; the present invention the above and other objectsare achieved by incorporating in the fuel certain stabilizing agents aswill be fully described hereinafter.

.We have found that gasolines containing a lead tetraethyl anti-knockreagent and which tend to become cloudy and eventually to form a whitedeposit in sunlight may be successfully stabilized by incorporating inthe gasoline a small proportion oi lecithin. v

The following results will show the efiect of lecithin. one, partiallycracked gasoline contain-- inglead tetraethyl or ethyl fluid and knownin the trade as Q gasoline and which is a grade -of gasoline containingnot more than 1.5 cc. of

ethyl-fluid per gallon and having a, maximum octane rating of 70, Thegasoline was copper, color due to the presence of a dye. The tests weremade by exposing a control sample and samples containing variousquantities of lecithin in glass containers to sunlight and notingthechange in cloudiness, color, gum formation and iur content" which oftenail'ects adversely the anti-knock value." I c o it? ill. 7 '35 7 p vControl is l6 s 3 Copper... Red--. 6 10 7o c1 7 Control-+7.5 lbs.lecithin 1% 2 3 -.do ..do 6 :39 70 64 I qgiii aam i ttilsemm f2 3 a no"do-" 4 4m 1o 65: 4o 7 (in ing-1 22.5 lbs. lecithin a an :s as a 4 g at70 o1 i Control-$37.5 lbs. numb an 4 a an an 4 55 7o \sc pcrlQOObbls.

stability of the gasoline in sunlight, particularly 4., in the presenceor a; lead anti-knockreagent.

An important object-oi. the present invention is to manufacture agasoline hydrocarbon motorfu'el containing an anti-knock reagent of thetetraethyl lead to stability, J q 1 Anotherobiect ofthe'inVention' is toprevent type which is of improved:

" or-retard deterioration in color, mum-orantiknockyalue of ananti-knock gasoline motor luel' containing a substantial proportion oi.un- 55 or. cracked It will be observed from the foregoing results thatit ispossible to stabilize the sasolineso that.

no cloud tor-motion occurs for various periods of tim'e by the addition01' the required quantity of lecithin. Thus, 15 lbs. per, 1000 barrelsoi. lecithin stabilize the gasoline for about 2 hours whereas theuntreated sample beco'mes cloudy in in the gasoline is of majorconsideration, the

lecithin is a valuable tool for stabilizing the gasoline. It has beenfound that, ingeneral, lecithin is more effective in inhibiting cloudformation in cracked gasoline than in straight run gasoline. It has alsobeen found that samples of gasoline containing eflective amounts oflecithin remain stable in storage for at least three months and whenthereafter exposed to slmlight, the samples are substantially as stableas before storage.

It is necessary in some cases, particularly in the treatment ofmorerefractory products, such as those containing large amounts of straightcause a bleaching eifect when added to samples I which were of poorcolor. a

It has now been found that by combining both the strong inhibitor andphenols with lecithin to form a mixture of a strong inhibitor, phenols,

and lecithin, a very desirable combination is obtained which not onlyprevents cloud formation, but also retards the deterioration in color,gum and anti-knock properties. The following results show the effect ofusing a mixture of lecithin, a strong gum inhibitor and petroleumphenols or cresylic acid in two samples of unstable Q grades ofgasoline.

Cloudand deposit ror- Gum formation Anti-knock mation, time in hours0010' changes mg./l cc. value Ve Heavy Clear After After Alter clou ydeposit Orig. Orig. Orlg. for 8MP 8 hrs. 8 hrs. 8 hrs.

Control No. l if; 4- 4 001313612.-. Salmon-.- 14 53 70 68- Control No.l+l lbs.lecithin+5 +8 o No change. 14 50 69 60 lbs. benzyl aminophenol+gals. cresylic acid per 1.000 bbls. Control No. 2 3f; 1% 4 do- Salmon. 858 67 66 Control No. 2+l5lbs.lecithin+5 +8 do No change. 16 33 67 66lbs. benzyl-aminophenol+l0 gals. crcsylic acid per 1,000 bbls. ControlNo. 2+15 lbs. lecit1|in+ +8 do do 10 30 66 7.5 lbs. benzyl-aminophenolg-bll'l gals. eresylie acid per 1,000

s. Control No. 2+l5 lbs. lecithin+ +8 do 11 24 66 66 7.5 lbs.pyrogallol+17 gals. cresylic acid per 1.000 bbls. Control No. 2+l5 lbs.lecithm+ +8 do ..do 14 34 67 66 6 lbs. benzyl-aminophenol+l0 gals.petroleum phenols per 1,000b ls. Control No. 2+l5 lbs. lec1thin+ +8...do....... do 16 32 66 66 5 lbs. pyrogallo1+10 gals. petroieum phenolsper 1,000 bbls.

run gasoline, to use more effective stabilizing reagents than lecithinalone and in an effort to find such a material, it was found thatacumbination of lecithin and a strong gum inhibitor, such asbenzyl-aminophenol, pyrogallol, butyryl pyrogallol, alpha and betanaphthol, catechol, triamylamine, etc. would give much better resultsthan lecithin alone. The following table shows the results obtained whenadding lecithin in combination with certain inhibitors to a Q gasolineconsisting largely of straight run gasoline and exposing the same tosunlight in glass containers.

Cloud and'deposit formation, time in hours Very Heavy g2 cloudy depositeiteralter- Control 3% 2 5 Control+15 lbs. lecithin per 1000 bbls. 2% 45 Control+16 lbs. lecithin+7.5 lbs. butyrl pyrogallol r 1000 bbls 4% 6 ZControl+l5 l s. lecithin-Hi gals. petroleum phenols pe 1000 hbls 6% 0 24Control-l- 15 lbs. lecithin-{4.5 lbs benzyleminophenol per 1000 bbls 24While the present invention is directed chiefly to stabilizing gasolinescontaining ananti-knock reagent against discoloration and formation of acloud or deposit in sunlight, nevertheless it. will be observed thatsome beneficial stabilizing effect on the gum and anti-knock propertiesmay also be obtained. The particular gasolines. herein treated wereparticularly unstable with respect to cloud and deposit formation andrelatively stable as to gum and anti-knock properties over periods ofthe extent of the present tests, but inv the case of gasolines which aremore unstable as to gum and'anti-knock properties or over more extendedperiods of storage, the present inhibitors may show greater value instabilizing the gum and anti-knock properties than the above resultsindicate, I

The present invention is advantageous for treating gasolines of highsulfur content such as those from South Texasand New Mexico crudes.

In the refining of such gasolines wherein the naphtha from which thegasoline is derived is acid treated and rerun it is often advantageousto sweeten before steam distillation'or both before and after. steamdistillation; however, even after such treatments the sulfur contentmaybe about 0.075 to 0.10 per cent. Such gasolines con-' taininganti-knock reagents areoften quite unstable and the present inventionprovides a particularly valuable method of treating these products,although gasolines of lower sulfur content may be advantageouslytreated.

The combinations of lecithin, a strong gum inhibitor and cresylic acidhave been found to be commercially valuable stabilizing reagents. Such acombination is very effective and each of the components appears to.have certain advantages.

of the anti-knock reagent and eliminate cloudi- Thus, the lecithin-tendstorretard decomposition ness and formation of deposits. The guminhibitor tends to augment the stabilizing effect of the lecithin andalso to perform a valuable inhibiting action with-respect to color, gumand anti-knock deterioration. s The cresylic acid or petroleum phenolsact as a mutual solvent and may replace acetone which is often used forthis purpose. The cresylic acid also exerts considerable stabilizingeffect on the color and facilitates the mixing of the inhibitor andgasoline to be treated. I

-, In practicing the. invention it is advantageous to dissolve thelecithin and gum inhibitor in the cresylic acid to form a stabilizerreagent and then add this reagent in the required amount to the gasolineto be treatedi The resulting mixture is ordinarily a liquid consistingof a solution of the lecithin and inhibitor dissolved in the cresylicacid. Such a mixture is easily handled and readily commingled'with thegasoline.

In case it .is desired to add the anti-knock'reagent and the stabilizerto the gasoline at the same time, we have found that a convenient andvaluable reagent may be prepared by mixing the two reagents together.Accordingly, we may com bine the reagents described above, consisting oflecithin,'lecithin and 'a gum inhibitor, or lecithin,

a gum inhibitor and cresylic acid, Wlththe lead tetraethyl anti-knockreagent or ethyl fluid in the proportions desired ,to be added tothetgasoline. Such a reagent is not only convenient to handle but alsothe stabilizer reagent has a-beneficial effect on the anti-knock reagentwhereby the latter is stabilized against decomposition. We have foundthat the anti-knock reagent so treated will keep for extended periods,of time without" decomposition or deposition of precipitates.

While we have obtained best results with petroleum phenols or phenolsrecovered from waste alkali liquors from treating cracked distillates,however, where petroleum phenols are not available, we may use othertypes of commercial mixtures of phenols, such as cresylic-acid, creosoteoil, carbolic-oil', etc.

v The petroleum phenols referred to above are the phenolic bodiesoccurring in varying amounts in most cracked petroleum distillates.These phenols may be extracted from the distillate by a caustic alkalior carbonate solution from which the phenols may be recovered by partialor complete acidification and separationtherefromjof the resultingphenol layer. In the ordinary course of refinery operation,.thesephenols are extracted from the cracked distillates by the refiningreagents, such as caustic alkali wash or doctor reagents. The-phenolsmay be conveniently recovered from such refinery liquors by blowing withflue gas or other means of efl'ecting neutralization sufficient toliberate the phenols.

It is usually advantageous to redistill the phenols to separate highboiling bodiessuch as; tar and asphalt. It is also sometimes desirableto fractionatethe phenols and use only the more desirable fractions forthe purposes of the present invention. I

we have. given examples o'f stabilizing agents which we have founduseful but we do not wish to be limited to thespeciflc amounts ofmaterials recited. One skilled in the art will obviously vary theamounts and proportions of the ingredients to give optimum results.

.We claim:

1. A stable antiknock motor fuel comprising gasoline and tetraethyllead, said motor fuel normally tending to deteriorate in sunlight andcontaining small amounts of lecithin and an arcmatic ring compoundsubstituted with one or more groups of the class of amino and hydroxy,

whereby such deterioration is substantially'retarded.

2. A composition according to claim 1 in which the aromatic ringcompound is alpha-naphthol. 3. A composition according to claim 1 inwhich the aromatic ring compound is benzyl-aminm phenol. I e

4. A composition according to claim 1 in which the aromatic ringcompound is pyrogallol.

5. A stable antiknock motor fuel comprising gasoline and tetraethyllead, said motor fuel nor-- mally tending to deteriorate in sunlight,and containing small amounts of lecithin, cresylic acid and an aromaticcompound substituted with one or more groups of the class of amino andhy-- droxy, whereby such deteriorationis substantially retarded.

6. The method of stabilizing, against deterioration in sunlight, anantiknock motor fuel com- .prising gasoline and tetraethyl lead, whichcomprises incorporating in the motor fuel small amounts of lecithin andan aromatic hydroxy compound substituted with one or more groups of theclass of amino and'hydroxy. 7. The method of stabilizing, againstdeterioration insunlight, an antiknock motor .fuel comprising gasolineand tetraethyl lead, which com-' prises incorporating in the motor fuelsmallamounts of lecithin, cresylic acid'and" an arc- "matic ringcompound substituted with one or more groups ofthe class of amino and.hydroxy. 8. A stable anti-knock motor fuel comprising gasoline and leadtetraethyl, said motor fuel normally tending to deteriorate insunlight,stabilized 9. A stable anti-knock motor fuel comprising 10. A stableanti-knock motor fuel comprising I Y gasoline and lead tetraethyl, saidmotor fuel nor--- mally tending to deteriorate in sunlight, stabilizedby containing small amounts of lecithin and benzyl .aminophenol. 11. Themethod of stabilizing, against deterioration in sunlight, anantiknockmotor fuel comprising gasoline and tetraethyl lead, which compri'sesadding to the fuel small amounts of lecithin and alphanaphthol.

12. The method of stabilizing; against deterioration in sunlightfanantiknock motor fuel comprising gasoline and tetraethyl lead,whichcomprises adding to the fuel'small amounts of lecithin and benzylaminophenol.

" HARRY V. REES.

JOI-IAN o. n. oos'raan'op'r.

